羟基锡酸盐载铂复合催化剂Pt/(Co,Zn)Sn(OH)_6的合成及其甲醇电催化氧化性能
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摘要
以羟基锡酸盐CoSn(OH)6和ZnSn(OH)6纳米空心立方体为前体,采用抗坏血酸作为弱还原剂,经过超声过程分别合成了羟基锡酸钴载Pt/CoSn(OH)6和羟基锡酸锌载Pt/ZnSn(OH)6复合催化剂,并在甲醇氧化反应(MOR)中表现出良好的性能。Pt/CoSn(OH)6和Pt/ZnSn(OH)6催化剂的单位质量活性分别为1 095.6mA/mg和699.5mA/mg,高于C载Pt(Pt/C)的594.6mA/mg。利用XRD、SEM、TEM、XPS和电化学测试对催化剂晶体结构和性能间的关系进行了探索。CO溶出实验结果表明,羟基锡酸盐载体有利于Pt表面CO的去除,载体与Pt间的强相互作用和载体表面的大量羟基基团增强了催化剂的催化活性和CO抗毒性。此外,Pt/(Co,Zn)Sn(OH)6催化剂中单质Pt高的相对含量也有利于提高MOR活性。通过研究载铂羟基锡酸盐电催化氧化甲醇性能,能够揭示载体结构对催化性能的影响,有助于羟基锡酸盐载铂复合催化剂在直接甲醇燃料电池(DMFCs)领域的应用。
The Pt/CoSn(OH)_6 and Pt/ZnSn(OH)_6 complex catalysts were prepared using CoSn(OH)_6 and ZnSn(OH)_6 hollow nanocubes by an ultrasound process with ascorbic acid as the soft reductant,respectively,and demonstrate excellent performance towards the methanol oxidation reaction(MOR).The Pt/CoSn(OH)_6 and Pt/ZnSn(OH)_6 catalysts exhibit higher mass activities(1095.6 mA/mg and 699.5 mA/mg,respectively)compared to Pt/C(594.6 mA/mg)catalyst towards methanol oxidation.XRD,SEM,TEM,XPS and electrochemical measurements were employed to explore the relationships of the crystal structure and the properties of catalysts.CO-stripping experiment results indicate that the hydroxide supports facilitates the removal of CO on Pt surface.The increased activity and resistance of CO poisoning for Pt/CoSn(OH)_6 and Pt/ZnSn(OH)_6 catalysts can be attributed to the strong interaction between the support(Co,Zn)Sn(OH)_6 and Pt in the catalysts and the large amount of hydroxyls on the support surface.The higher relative intensity of Pt in the(Co,Zn)Sn(OH)_6 catalysts also contrib-utes to the higher MOR activity.The(Co,Zn)Sn(OH)_6 towards methanol catalytic electro-oxidation can disclose the influence of the support structure on the catalytic activity and will be helpful for the development and application of complex catalysts in direct methanol fuel cells(DMFCs).
The Pt/CoSn(OH)_6 and Pt/ZnSn(OH)_6 complex catalysts were prepared using CoSn(OH)_6 and ZnSn(OH)_6 hollow nanocubes by an ultrasound process with ascorbic acid as the soft reductant,respectively,and demonstrate excellent performance towards the methanol oxidation reaction(MOR).The Pt/CoSn(OH)_6 and Pt/ZnSn(OH)_6 catalysts exhibit higher mass activities(1095.6 mA/mg and 699.5 mA/mg,respectively)compared to Pt/C(594.6 mA/mg)catalyst towards methanol oxidation.XRD,SEM,TEM,XPS and electrochemical measurements were employed to explore the relationships of the crystal structure and the properties of catalysts.CO-stripping experiment results indicate that the hydroxide supports facilitates the removal of CO on Pt surface.The increased activity and resistance of CO poisoning for Pt/CoSn(OH)_6 and Pt/ZnSn(OH)_6 catalysts can be attributed to the strong interaction between the support(Co,Zn)Sn(OH)_6 and Pt in the catalysts and the large amount of hydroxyls on the support surface.The higher relative intensity of Pt in the(Co,Zn)Sn(OH)_6 catalysts also contrib-utes to the higher MOR activity.The(Co,Zn)Sn(OH)_6 towards methanol catalytic electro-oxidation can disclose the influence of the support structure on the catalytic activity and will be helpful for the development and application of complex catalysts in direct methanol fuel cells(DMFCs).
引文
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[2]YANG J,LIU D.Three dimensionally structured electrode assembly for proton-exchange membrane fuel cell based on patterned and aligned carbon nanotubes[J].Carbon,2007,45(14):2845-2848.
[3]WASMUS S,KVER A.Methanol oxidation and direct methanol fuel cells:A selective review[J].Journal of Electroanalytical Chemistry,1999,461(1-2):14-31.
[4]MEHMOOD A,SCIBIOH M A,PRABHURAM J,et al.A review on durability issues and restoration techniques in longterm operations of direct methanol fuel cells[J].Journal of Power Sources,2015,297:224-241.
[5]WANG J,YIN G,SHAO Y,et al.Effect of carbon black support corrosion on the durability of Pt/C catalyst[J].Journal of Power Sources,2007,171(2):331-339.
[6]HU Y,ZHU A,ZHANG C,et al.Microwave-assisted synthesis of double-shell PtRu/TiO2catalyst towards methanol electro-oxidation[J].International Journal of Hydrogen Energy,2015,40(45):15652-15662.
[7]CHAKROUNE N,VIAU G,AMMAR S,et al.Acetate-and thiol-capped monodisperse ruthenium nanoparticles:XPS,XAS,and HRTEM studies[J].Langmuir,2005,21(15):6788-6796.
[8]ANTOLINI E.Carbon supports for low-temperature fuel cell catalysts[J].Applied Catalysis B:Environmental,2009,88(1-2):1-24.
[9]LAMY C,LIMA A,LERHUN V,et al.Recent advances in the development of direct alcohol fuel cells(DAFC)[J].Journal of Power Sources,2002,105(2):283-296.
[10]ITO Y,TAKEUCHI T,TSUJIGUCHI T,et al.Ultrahigh methanol electro-oxidation activity of PtRu nanoparticles prepared on TiO2-embedded carbon nanofiber support[J].Journal of Power Sources,2013,242:280-288.
[11]FENG C,TAKEUCHI T,ABDELKAREEM M A,et al.Carbon-CeO2composite nanofibers as a promising support for a PtRu anode catalyst in a direct methanol fuel cell[J].Journal of Power Sources,2013,242:57-64.
[12]ZHANG J,TU J,DU G,et al.Pt supported self-assembled nest-like-porous WO3hierarchical microspheres as electrocatalyst for methanol oxidation[J].Electrochimica Acta,2013,88:107-111.
[13]韩朝辉,竺培显,郭佳鑫,等.二组元(RuO2-TiO2)及三组元(RuO2-SnO2-TiO2)Ti阳极涂层的微观组织对其电化学性能的影响[J].复合材料学报,2013,30(6):121-126.HAN Z H,ZHU P X,GUO J X,et al.Effects of microstructures of Ti anode coating with two constituents(RuO2-TiO2)and three constituent(RuO2-SnO2-TiO2)on the electrochemical properties[J].Acta Materiae Compositae Sinica,2013,30(6):121-126(in Chinese).
[14]TAMMAM R H,FEKRY A M,SALEH M M.Electrocatalytic oxidation of methanol on ordered binary catalyst of manganese and nickel oxide nanoparticles[J].International Journal of Hydrogen Energy,2015,40(1):275-283.
[15]HUANG D,FU X,LONG J,et al.Hydrothermal synthesis of MSn(OH)6(M=Co,Cu,Fe,Mg,Mn,Zn)and their photocatalytic activity for the destruction of gaseous benzene[J].Chemical Engineering Journal,2015,269:168-179.
[16]HUANG F,YUAN Z Y,ZHAN H,et al.A novel tin-based nanocomposite oxide as negative-electrode materials for Li-ion batteries[J].Materials Letters,2003,57(22-23):3341-3345.
[17]LUO B,XU S,YAN X,et al.Graphene nanosheets supported hollow Pt&CoSn(OH)6 nanospheres as a catalyst for methanol electro-oxidation[J].Journal of Power Sources,2012,205:239-243.
[18]GUO D,CUI S.Hollow PtCo nanospheres supported on multi-walled carbon nanotubes for methanol electrooxidation[J].Journal of Colloid and Interface Science,2009,340(1):53-57.
[19]李赵华,刘成宝,钱君超,等.超级电容器用CEO2-MNO/3D石墨烯复合材料的制备[J].复合材料学报,2017,34(2):423-429.LI J H,LIU C B,QIAN J C,et al.Synthesis of CeO2-MnO/3Dgrapheme composite for supercapacitors[J].Acta Materiae Compositae Sinica,2017,34(2):423-429(in Chinese).
[20]YANG J,DEIVARAJ T C,TOO H,et al.An alternative phase-transfer method of preparing alkylamine-stabilized platinum nanoparticles[J].Journal of Physical Chemistry B,2004,108(7):2181-2185.
[21]BISHT A,ZHANG P,SHIVAKUMARA C,et al.Pt-doped and Pt-supported La1-xSrxCoO3:Comparative activity of Pt4+and Pt0toward the CO poisoning effect in formic acid and methanol electro-oxidation[J].Journal of Physical Chemistry C,2015,119(25):14126-14134.
[22]HAN D M,GUO Z P,ZENG R,et al.Multiwalled carbon nanotube-supported Pt/Sn and Pt/Sn/PMo12electrocatalysts for methanol electro-oxidation[J].International Journal of Hydrogen Energy,2009,34(5):2426-2434.
[23]LGER J M,ROUSSEAU S,COUTANCEAU C,et al.How bimetallic electrocatalysts does work for reactions involved in fuel cells?:Example of ethanol oxidation and comparison to methanol[J].Electrochimica Acta,2005,50(25-26):5118-5125.
[24]HIGGINS D,HOQUE M A,SEO M H,et al.Development and simulation of sulfur-doped graphene supported platinum with exemplary stability and activity towards oxygen reduction[J].Advanced Functional Materials,2014,27(24):4325-4336.
[25]MU Y,LIANG H,HU J,et al.Controllable Pt nanoparticle deposition on carbon nanotubes as an anode catalyst for direct methanol fuel cells[J].Journal of Physical Chemistry B,2005,109(47):22212-22216.
[26]CHEN X,SI C,GAO Y,et al.Multi-component nanoporous platinum-ruthenium-copper-osmium-iridium alloy with enhanced electrocatalytic activity towards methanol oxidation and oxygen reduction[J].Journal of Power Sources,2015,273:324-332.
[27]RUAN D,GAO F,GU Z.Enhanced electrochemical properties of surface roughed Pt nanowire electrocatalyst for methanol oxidation[J].Electrochimica Acta,2014,147:225-231.